WO2002076605A1 - Procede de production de capsules - Google Patents

Procede de production de capsules Download PDF

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Publication number
WO2002076605A1
WO2002076605A1 PCT/EP2002/003155 EP0203155W WO02076605A1 WO 2002076605 A1 WO2002076605 A1 WO 2002076605A1 EP 0203155 W EP0203155 W EP 0203155W WO 02076605 A1 WO02076605 A1 WO 02076605A1
Authority
WO
WIPO (PCT)
Prior art keywords
oil
core material
methyl
encapsulation
encapsulations
Prior art date
Application number
PCT/EP2002/003155
Other languages
German (de)
English (en)
Inventor
Forian Wolf
Gerd Mansfeld
Falk Harzke
Jörg Eilers
Dirk MÜLLER
Original Assignee
Symrise Gmbh & Co. Kg
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE10114509A external-priority patent/DE10114509A1/de
Application filed by Symrise Gmbh & Co. Kg filed Critical Symrise Gmbh & Co. Kg
Publication of WO2002076605A1 publication Critical patent/WO2002076605A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/70—Fixation, conservation, or encapsulation of flavouring agents
    • A23L27/72—Encapsulation
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P10/00—Shaping or working of foodstuffs characterised by the products
    • A23P10/30—Encapsulation of particles, e.g. foodstuff additives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
    • A61K9/16—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction
    • A61K9/1605—Excipients; Inactive ingredients
    • A61K9/1629—Organic macromolecular compounds
    • A61K9/1635—Organic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyvinyl pyrrolidone, poly(meth)acrylates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/70—Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • A61L9/014—Deodorant compositions containing sorbent material, e.g. activated carbon
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/015—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
    • A61L9/02—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air by heating or combustion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/025—Applications of microcapsules not provided for in other subclasses

Definitions

  • the invention relates to a method for producing and applying encapsulations containing at least one film-forming polymer and core material
  • the present invention describes the encapsulation of material to be encapsulated (core material) with polymeric film-forming encapsulation material (film-forming polymer), a flowable mixture comprising core material, polymeric film-forming encapsulation material and at least one organic solvent being applied to a surface.
  • This flowable mixture hardens on this surface by removing the solvent, whereby an encapsulation which adheres to the surface and contains the core material is formed.
  • Encapsulation of, for example, drugs, pesticides, vitamins, or smells and flavors, is done for a variety of reasons.
  • active components especially in the field of medicine and
  • the encapsulation can bring about a controlled release of the active ingredients.
  • the encapsulation may like the vitamins before degradation reactions such as Air oxidation, protect and thereby increase the life of the vitamins.
  • the encapsulation enables a form which is easy to handle, is stable in storage and only allows controlled release when used, for example by the action of water.
  • encapsulations can be in the form of a coating (film) or in spatially isolated form (capsule).
  • film a coating
  • capsule a spatially isolated form
  • encapsulation methods and suitable materials are known from the literature.
  • sucralose with polyvinyl acetate for use in chewing gum is known from EP 454 829 B1 and WO 91/07103.
  • DE 4239082 describes layer supports with microencapsulated fragrances, the capsules being fixed on the support by means of a binder.
  • EP 831384 describes, for example, an aroma storage unit which, in a special embodiment, uses an aroma-causing agent which is embedded in a binder material.
  • Core material of the encapsulation the discontinuity of the process, the non-uniformity of the particle surfaces and sizes, the equipment and technical complexity, the use of aqueous solutions or emulsions, a complex post-processing, sieving of the encapsulation or the considerable diffusion of the core material out of the encapsulation. It is also a complex step that requires additional means, such as binders, if the capsules are to be fixed on a surface.
  • the object was therefore to find a process which allows the production and application of an encapsulation on a surface, wherein the core material can be encapsulated without thermal stress in such a way that there is a hard encapsulation at room temperature.
  • the shape, extension and size of the encapsulation should be easy to influence and control, and it should be technically easy to carry out in order to enable a narrow distribution of the capsule size.
  • Encapsulation and application to surfaces should be such that the
  • Encapsulation adheres very well to the surface (self-adhesion) and a targeted release of the core material takes place at slow, moderate or fast speed as required. Avoiding additives such as emulsifiers is preferred.
  • the process is intended to enable a high loading of the encapsulation with core material.
  • the present invention therefore relates to a process for the production of encapsulations on surfaces, characterized in that film-forming polymer and core material are taken up in at least one solvent, this flowable mixture is applied to a surface and then dried.
  • the present invention also relates to surfaces containing encapsulations, characterized in that the encapsulations contain fragrances, flavors or nicotine and at least one film-forming polymer.
  • the present invention furthermore relates to the use of the encapsulations produced according to the invention for the thermal release of the core material, the use of the encapsulations according to the invention for the individual, personal application of the core material and the use of the encapsulations comprising surfaces comprising nicotine in a process for weaning smokers.
  • Natural and synthetic non-chlorinated polymers are suitable as polymeric film-forming encapsulation materials.
  • One or more of the polymers mentioned can be used as encapsulation material in the process according to the invention.
  • Suitable natural film-forming polymers are, for example, chitosan with a molecular weight of 20,000 to about 5 million g / mol, chitin derivatives, chitosan derivatives, partially or completely neutralized shellac, various types of saccharides such as polysaccharides or mixtures of oligo- or mono - And disaccharides, which are sold, for example, by the Cerestar company under the name C-PUR.
  • Other suitable natural polymers are Chinese balsam resin and cellulose derivatives, e.g. Hydroxypropyl cellulose with a molecular weight of 30,000 to 50,000 g / mol.
  • Suitable film-forming anionic polymers are synthetic homopolymers or copolymers with monomer units containing neutralizable acid groups, which are optionally copolymerized with comonomers which contain no acid groups. As acid groups come sulfonic, phosphoric and
  • Suitable monomers containing acid groups are, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid or maleic anhydride, aldehyde carboxylic acids or ketocarboxylic acids.
  • Comonomers which are not substituted with acid groups are, for example, acrylamide,
  • Suitable film-forming anionic polymers are in particular uncrosslinked homopolymers of acrylic acid or those crosslinked with polyfunctional agents
  • Methacrylic acid copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid or methacrylic acid with monomers selected from acrylic acid or methacrylic acid esters, acrylamides, methacrylamides and vinyl pyrrolidone, homopolymers of crotonic acid and copolymers with monomers selected from vinyl esters, acrylic acid or methacrylic acid esters, acrylamides and methacrylamides, copolymers based on alkyl vinyl ethers and maleic acid monoalkyl esters, copolymers of maleic anhydride and polyvinyl methyl ether.
  • polymers with acid groups are crosslinked or uncrosslinked vinyl acetate-crotonic acid copolymers, as well as terpolymers made from vinyl acetate, crotonic acid and polyethylene oxide and terpolymers made from acrylic acid, alkyl acrylate and N-alkylacrylamide, especially acrylic acid-ethyl acrylate-Nt-butylacrylamide terpolymers or t-butylacrylamide.
  • Another class of suitable film-forming polymers are polyurethanes.
  • Suitable anionic polyurethanes are characterized, for example, by the fact that (a) they have terminal acid groups which have been introduced, for example, via aminosulfonic acids or aminocarboxylic acids, (b) optionally contain further free carboxylic acid groups which have been introduced as comonomers by polymerizing in carboxylic acid diols such as, for example, dimethylolpropanoic acid (c) Contain polyurethane sequences which have been formed from polyester diols and diisocyanates such as, for example, alkylene diisocyanates or isophorone diisocyanate.
  • Suitable synthetic, nonionic, film-forming polymers are for example
  • Nonionic monomers are e.g. Acrylamide, methacrylamide, alkyl and dialkyl acrylamide, alkyl and dialkyl methacrylamide, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, vinyl pyrrolidone, vinyl ester, vinyl alcohol, propylene glycol or ethylene glycol, the alkyl groups of these monomers preferably having C 1 -C 7 -alkyl groups, particularly preferably C 1 -C 4 C3 are alkyl groups.
  • Suitable synthetic, nonionic, film-forming polymers are in particular homopolymers of vinylpyrrolidone, vinylcaprolactone and N-vinylformamide, copolymers of vinylpyrrolidone and vinyl acetate, copolymers of vinylpyrrolidone and vinylimidazole, terpolymers of vinylpyrrolidone,
  • Suitable amphoteric film-forming polymers are, for example, copolymers of octyl acrylamide, butylaminomethacrylate and acrylate, copolymers of octylacrylamide, t-butylaminoethyl methacrylate and two or more monomers consisting of acrylic acid, methacrylic acid or their esters.
  • copolymers of acrylic acid, methacrylate and methacrylamidopropyltrimethylammonium chloride are copolymers of acrylic acid, methacrylate and methacrylamidopropyltrimethylammonium chloride.
  • Suitable cationic film-forming polymers are, for example, polyvinylpyrrolidone-dimethylaminoethyl methacrylate copolymer, a terpolymer made from vinylpyrrolidone, dimethylaminoethyl methacrylate and vinylcaprolactam, vinylpyrrolidone-methacrylamidopropyltrimethylammonium chloride copolymer and in particular a copolymer made from polyvinylpyrrolidone and imidazolimino chloro.
  • the polysiloxanes are preferred.
  • Polysiloxanes which are solid at room temperature, polysiloxane-polyether copolymers, polyalkylsiloxanes or diquarternary polydialkylsiloxanes may be mentioned here, for example.
  • film-forming polymers preference is given to those which contain vinylcaprolactone, vinylpyrrolidone or vinyl acetate, particularly preferably those which contain vinylpyrrolidone or vinyl acetate, and in turn preferred are polymers, in particular copolymers containing vinylpyrrolidone and
  • Preferred representatives of the preferred film-forming polymers are: vinylimidazole-vinylpyrrolidone copolymers, vinylpyrrolidone homopolymers, vinylcaprolactone homopolymers, vinylpyrrolidone-vinyl acetate copolymers, vinylpyrrolidone-
  • Vinyl acetate-vinyl propionate terpolymers in particular vinylimidazole-vinylpyrrolidone copolymers, vinylpyrrolidone homopolymers, vinylpyrrolidone-vinyl acetate copolymers.
  • the vinylpyrrolidone-vinyl acetate copolymers have proven to be particularly suitable. In the copolymers of vinyl pyrrolidone and vinyl acetate, ratios of vinyl pyrrolidone are too
  • Vinyl acetate in the range of 7: 3 for example, Luviskol ® VA 73, BASF
  • 3: 7 such as Luviskol ® VA 37, BASF
  • the film-forming polymers can have a mass fraction in the mixture with core material and solvent of 10 to 90%, preferably 20 to 70% and particularly preferably 30 to 50%.
  • the core materials to be encapsulated according to the invention can contain: medicinal active substances, crop protection agents (for example insecticides, herbicides, fungicides), antibacterial, disinfectant or care agents, cosmetic substances, fragrances, flavorings (aromas), oils, silicone oils, vitamins,
  • Dyes stabilizers, antioxidants, preservatives, light stabilizers, UV absorbers, opacifiers, thickeners such as thickening polymers or silica gels, hardness modifiers such as crosslinking agents and others.
  • Core materials which are particularly advantageous according to the invention are volatile, preferred
  • Core materials contain fragrances, flavors or nicotine.
  • the finished encapsulations consist only of encapsulation material and one or more fragrances, flavorings or nicotine and possibly small amounts of the solvent which has not been completely removed.
  • chlorinated polymers such as PVC
  • PVC chlorinated polymers
  • Fragrances and flavors are mostly complex mixtures of generally volatile components, which are also often sensitive to temperature.
  • fragrances that can be part of the core material can be found, for example, in K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 3 rd . Ed., Wiley-VCH, Weinheim 1997. The following may be mentioned in detail:
  • Extracts from natural raw materials such as essential oils, concretes, absolute,
  • Resins, resinoids, balms, tinctures such as B. Ambratincture; Amyrisöl; Angelica seed oil; Angelica root oil; anise oil; Valerian oil; Basil oil; Baummoos -Absolue; Bay oil; Mugwort oil; Benzoeresin; Bergamot oil; Beeswax absolute; birch tar;
  • camphor oil camphor oil
  • Cananga oil cardamom; Cascarillaöl; cassia; Cassie absolute;
  • copaiba balsam ; Copaivabalsamöl; Coriander oil; costus root; Cuminöl; Cypress oil; Davanaöl; Dill herb oil; Dill seed oil; Eau de brouts - absolute; Oak moss absolute; elemi; Tarragon oil; Eucalyptus citriodora oil; eucalyptus oil;
  • Fennel oil Pine needle oil; galbanum; Galbanumresin; geranium; Grapefruit oil;
  • guaiac wood gurjun balsam
  • gurjun balsam oil Helichrysum absolute; Helichrysum oil; Ginger oil; Iris root absolute; Orris root oil; Jasmine absolute; calamus; Chamomile oil blue; Roman chamomile oil; Carrot seed oil; Kaskarillaöl; Pine needle oil;
  • Lavandin absolute Lavandin oil; Lavender absolute; Lavender oil; Lemongrass oil; Loving stick oil; Distilled lime oil; Lime oil pressed; linaloe; Litsea cubeba oil;
  • Bay leaf oil ; Macisöl; Marjoram oil; Mandarin oil; Massoirindenöl; Mimosa absolute; Musk seed oil; musk tincture; Clary sage oil; nutmeg;
  • Olibanum absolute olibanum
  • Opopanaxöl Orange blossom absolute
  • Orange oil
  • Palmarosa oil palmarosa oil; patchouli oil; perilla oil; Peruvian balsam oil; Parsley leaf oil;
  • Parsley seed oil Parsley seed oil; Petitgrain oil; Peppermint oil; Pepper oil; chilli; pine oil; Poleyöl; Rose absolute; Rosewood oil; Rose oil; Rosemary oil; Dalmatian sage oil; Sage oil spanish; sandalwood; Celery seed oil; spike lavender oil; star anise; Styraxöl;
  • aliphatic alcohols such as e.g. hexanol; octanol; 3-octanol; 2,6-dimethyl-heptanol; 2-methylheptanol, 2-methyloctanol; (E) -2-hexenol; (E) - and (Z) -3-hexenol; l-octen-3-ol; Mixture of 3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E, Z) -2,6-Nonadienol; 3J-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol; the aliphatic aldehydes and their 1,4-dioxacycloalken-2-ones such as e.g.
  • aliphatic ketones and their oximes such as 2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone oxime; 2,4,4,7-
  • Tetramethyl-6-octen-3-one Tetramethyl-6-octen-3-one; the aliphatic sulfur-containing compounds such as e.g. 3-methylthiohexanol; 3-Methylthiohexylacetat; 3-mercaptohexanol; 3-mercapto-hexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; l-menthene-8-thiol;
  • aliphatic nitriles such as e.g. 2-nonenoic acid nitrile; 2-Tridecen Textrenitril;
  • aliphatic carboxylic acids and their esters such as e.g. (E) - and (Z) -3-hexenyl formate; ethylacetoacetate; isoamyl; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3
  • acyclic terpene alcohols such as e.g. citronellol; geraniol; nerol; linalool; Lavadulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyl octane-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadiene-2-ol; 2,6-dimethyl-3,5-octadiene-2-ol; 3J-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5J-octatrien-3-ol 2,6-dimethyl-2,5J-octatrien-l-ol; as well as their formates, acetates, propionates, isobuty
  • acyclic terpene aldehydes and ketones such as e.g. geranial; neral; citronellal;
  • cyclic terpene alcohols such as e.g. Menthol; isopulegol; alpha-terpineol;
  • cyclic terpene aldehydes and ketones such as menthone; menthone; 8-mercaptomenthan-3-one; carvone; camphor; fenchon; alpha-ionone; beta-ionone; alpha-n-methylionone; beta-n-methylionone; alpha-isomethylionone; beta-isomethyl ionone; alpha-irone; alpha-damascone; beta-damascone; beta-damascenone; delta-damascon; gamma-damascone; l- (2,4,4-trimethyl-2-cyclohexen-l-yl) -2-buten-l-one; l, 3,4,6J, 8a-hexahydro-l, l, 5,5-tetramethyl-2H-2,4a-methanonaphthalen-8 (5H) -one; nootkatone; Dihydronootkaton; alpha-sinen
  • cyclic alcohols such as e.g. 4-tert.-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isocamphylcyclohexanol; 2,6,9-trimethyl-Z2, Z5, E9-cyclododecatrien-1 -ol; 2-isobutyl-4-methyl tetrahydro-2H-pyran-4-ol;
  • cycloaliphatic alcohols such as e.g. alpha, 3,3-trimethylcyclohexylmethanol
  • cyclic and cycloaliphatic ethers such as e.g. cineol; cedryl methyl ether;
  • cyclic ketones such as 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-l-one; 3-methyl-cis-2-penten-l-yl-2-cyclopenten-l-one; 3-methyl-2-pentyl-2-cyclopenten-l -one; 3-methyl-4-cyclopentadecenone; 3-methyl-5-cyclopentadecenone; 3-methylcyclopentadecanone; 4- (1-ethoxyvinyl) -3, 3,5,5-tetra-methylcyclohexanone; 4-tert.-pentylcyclohexanone; 5-cyclohexadecen-l-one; 6,7-dihydro-l, l, 2,3,3-pentamethyl-4 (5H) -indanone; 5-cyclohexadecen
  • cycloaliphatic ketones such as e.g. l- (3,3-dimethylcyclohexyl) -4-penten-l-one; 1 - (5,5-Dimefhyl-1 -cyclohexen- 1 -yl) -4-penten-1 -one; 2,3,8,8-tetramethyl-l, 2,3,4,5,6J, 8-octahydro-2-naphthalenyl methyl ketone; Methyl 2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone; tert-butyl (2,4-dimethyl-3-cyclohexen-l-yl) ketone;
  • esters of cyclic alcohols such as e.g. 2-tert-butylcyclohexyl acetate; 4-tert butyl cyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; Deca- hydro-2-naphthylacetate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; Decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate; 4,7-mefhano-3a, 4,5,6,7,7a-hexahydro-5, or 6-indenyl acetate; 4J-methano-3a, 4,5,6JJa-hexahydro-5, or 6-indenylpropionate;
  • ester of cycloaliphatic carboxylic acids such as. B. allyl-3-cyclohexylpropionate; Allylcyclohexyloxyacetat; methyldihydrojasmonate; methyl jasmonate; Methyl 2-hexyl-3-oxocyclopentane carboxylate; Ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; Ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; Ethyl 2-methyl-1,3-dioxolane-2-acetate;
  • aromatic hydrocarbons such.
  • araliphatic alcohols such as e.g. benzyl alcohol; 1-phenylethyl;
  • esters of araliphatic alcohols and aliphatic carboxylic acids such as; benzyl acetate; benzylpropionate; benzyl isobutyrate; Benzylisovalerianat; 2-phenyl ethyl acetate; 2-phenylethyl propionate; 2-Phenylethylisobutyrat; 2-phenylethyl isovalerianate; 1-phenylethyl acetate; alpha-Trichlormethylbenzylacetat; alpha, alpha-dimethylphenyl ethyl acetate; alpha, alpha-Dimethylphenylethylbutyrat; Cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate; the araliphatic ether such as e.g.
  • aromatic and araliphatic aldehydes such as e.g. benzaldehyde; Phenyl acetaldehyde; 3-phenylpropanal; Hydratropaaldehyd; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3- (4-ethylphenyl) -2,2-dimethylpropanal; 2-methyl-3- (4-isopropylphenyl) propanal; 2-Methyl-3- (4-tert-butylphenyl) propanal; 3- (4-tert-butylphenyl) propanal; cinnamic aldehyde; alpha-Butylzimtaldehyd; alpha amyl cinnamon aldehyde; alpha-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-Hydroxy-3-methoxybenzaldehyde; 4-
  • aromatic and araliphatic ketones such as acetophenone; 4-methyl acetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4- (4-hydroxyphenyl) -2-butanone; 1 - (2-naphthalenyl) ethanone; benzophenone; 1, 1, 2,3, 3, 6-hexamethyl-5-indanyl methyl ketone; 6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone; 1 - [2,3-dihydro-1, 1, 2,6-tetramethyl-3- (l -methylethyl) - lH-5-indenyl] ethanone; 5 ', 6'J', 8'-tetrahydro-3 ', 5', 5 ', 6', 8 ⁇ , 8'-hexamethyl-2-aceto-naphthon;
  • aromatic and araliphatic carboxylic acids and their esters such as e.g. benzoic acid; phenylacetic acid; methylbenzoate; ethyl benzoate; hexyl benzoate;
  • Benzyl benzoate methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; Phenylethyl phenylacetate; Methylcinnmat; ethylcinnamate; Benzyl; Phenyl ethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; Isoamyl salicylate; hexyl salicylate; cyclohexyl; Cis-3-hexenyl salicylate; Benzyl salicylate; phenylethyl; Methyl-2,4-dihydroxy-3,6-dimethylbenzoate; Ethyl 3-phenyl glycidate; Ethyl-3-methyl-3-phenylglycidate;
  • the nitrogenous aromatic compounds such as e.g. 2,4,6-trinitro-l, 3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert.-butylacetophenone; cinnamic acid; 5-phenyl-3-methyl-2-penten Aciditril; 5-phenyl-3-methylpentanoic acid nitrile; methyl anthranilate; Methyl N-methylanthranilate; See bases of methylanthranilate with 7-hydroxy-3J-dimethyloctanal, 2-methyl-3- (4-tert-butylphenyl) propanal or 2,4-dimethyl-3-cyclohexenecarbaldehyde; 6-Isopropyl; 6-Isobutylchinolin; 6-sec-butylquinoline; indole; skatol; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-me
  • phenols, phenyl ethers and phenyl esters such as e.g. estragole; anethole; eugenol; Eugenylmethylether; isoeugenol; Isoeugenylmethylether; thymol; carvacrol; diphenyl ether; beta-Naphfhylmethylefher; beta-Naphthylethylether; beta-naphthyl isobutyl ether; 1,4-dimethoxybenzene; Eugenylacetat; 2-methoxy-4-methyl phenol;
  • heteroeyclic compounds such as 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one; the lactones such as 1,4-octanolide; 3-methyl-l, 4-octanolide; 1,4-nonanolide; 1,4-decanolide; 8-decen-l, 4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide; 1,5-dodecanolide; 1.15 pentadecanolide; ice and trans-l l-pentadecene-l, 15-olide; cis- and trans-12-pentadecene-1,15-olide; 1,16-hexadecanolide; 9-hexadecene-l, 16-olide;
  • fragrances and / or flavorings a repeatable, i.e. multiple, and individual fragrance presentation for people.
  • the fragrance application and thus the fragrance experience can be controlled, i.e. limited in time and adjustable according to intensity.
  • This fragrance presentation enables the fragrance as a further sensory dimension in the sense of enriching perception.
  • This fragrance presentation can be used, for example, in the scenting of cinema films, plays, performances on the Internet, television and video films, exhibitions and museums, radio broadcasts or also in the scenting of (interactive) software products, e.g. on computers.
  • the mass fraction of the core material in the mixture with solvent and film-forming polymer is typically 1 to 60%, preferably 10 to 40%, particularly preferably 15 to 25%.
  • Dispersions are used for the encapsulation process according to the invention, solutions are preferred.
  • aqueous solvents With some dosing systems it is advantageous to use aqueous solvents. Should the flowable mixture, for example, by means of piezoelectric Actuators are brought to the surface, water as a solvent or a high water content in the solvent is advantageous.
  • solvent mixtures are used, mixtures of a water-miscible organic solvent and
  • Water can be used.
  • the water content of these mixtures is preferably ⁇ 50% by weight, particularly preferably ⁇ 25% by weight, based on the solvent mixture.
  • Non-aqueous, flowable mixtures in the encapsulation process according to the invention mean mixtures which contain less than 5, preferably less than 2% by weight of water.
  • Organic solvents are particularly suitable as solvents.
  • Organic solvents with a boiling point ⁇ 200 ° C. are preferred, particularly preferred solvents with a boiling point ⁇ 100 ° C., which in turn are preferably oxygen-containing solvents.
  • the boiling points relate to normal pressure.
  • solvents that do not contain chlorine, bromine or iodine are particularly suitable.
  • Suitable organic solvent classes are, for example, cyclic or acyclic dialkyl, diaryl or alkylaryl ethers, aliphatic or aromatic
  • Hydrocarbons cyclic or acyclic dialkyl, diaryl or alkylaryl ketones, primary, secondary or tertiary alcohols, carboxylic acid esters.
  • alkyl residues contained in these solvents can be branched or unbranched.
  • Preferred solvents are alcohols, ketones or esters with 2 to 6 carbon atoms, preferably acetone, methyl ethyl ketone, ethanol, isopropanol and
  • Halogenated solvents such as, for example, chloromethane, dichloromethane, trichloromethane, carbon tetrachloride, chloroethane, dichloroethanes, trichloroethanes, tetrachloroethanes, generally chloroalkanes or chlorofluorocarbons are suitable, although not preferred.
  • the mass fraction of the solvent in the flowable mixture is typically 10 to 90%, preferably 20 to 70% and particularly preferably up to 30 to 50%.
  • All flowable mixtures of encapsulation material, core material and solvent can be used according to the invention. Mixtures of encapsulation material, core material and solvent with a viscosity of less than 10,000 mPas are advantageous. Mixtures with a viscosity of less than 5,000 mPas are particularly advantageous, a viscosity in the range from 50 to 3,000 mPas and particularly preferably in the range from 100 to 1,500 mPas is preferred.
  • the viscosity was determined using a falling body viscometer (ball-drop method). The measurements were carried out using the "Micro Visko 2" device from Haake at 24.5 ° C. using a 2.5 mm ball.
  • the proportion of the core material can be up to 65% by weight, typically the proportion of the core material is 5 to 55% by weight, preferably in the range 10 to 35% by weight.
  • the nicotine content is preferably in the case of encapsulations containing nicotine
  • a mass ratio of film-forming polymer, solvent and core material in the range from 25-50: 30-50: 10-25 is especially preferred in the range 40 - 45: 40 - 45: 15 - 20.
  • surfaces become hard or soft
  • temperature-stable surfaces are surfaces with a melting point above 150 ° C., preferably above 250 ° C. and particularly preferably above 300 ° C.
  • the surfaces can be smooth or contain depressions or recesses such as depressions, corrugations or grooves.
  • the encapsulations can be wholly or partially in or on the surface.
  • Examples of surface materials are metal, wood, glass, ceramics, clay,
  • Particularly suitable materials for the surfaces in the process according to the invention are aluminum-containing, iron-containing, nickel-containing, titanium-containing, molybdenum-containing
  • Metal compounds or alloys, polymer-containing surfaces, glass or cellulose-containing materials are used.
  • the surfaces can be components of any objects or devices. Suitable surfaces are, for example, household surfaces, furniture surfaces,
  • Kitchen furnishings household items and utensils, walls, doors, floors, lamps, windows, window frames, vehicle parts and surfaces, everyday items, items for use in personal surroundings, items for single use.
  • foils for example: foils, foils with high temperature stability, credit cards, plastic plants, wooden and stone floors, tiles, picture materials, cardboards, magazines, tables, chairs, fabric softener sheets, facial tissues, insect repellent devices, incandescent lamps, air conditioning systems , Glass plates, game biting devices, animal holding devices,
  • the encapsulation can be present as a coating (film) in any layer thickness or with a spatially isolated one Encapsulation (capsule) the spatial extent of the capsule produced by this method can be designed in any size and shape. Balls, spheres, disks or strips may be mentioned as examples of forms of the capsules which can be produced according to the invention.
  • Parameters such as viscosity, amount, composition of the mixture of encapsulation material, solvent and core material, shape and diameter of the metering opening, type and mode of operation of the metering system can be optimally adapted to the respective application.
  • the size of the capsules is typically in the range 0.05 to 20 mm, preferably in the range 0.5 to 5 mm.
  • the capsule size is preferably in the range 0.05 to 4 mm, particularly preferably in the range 0.1 to 2.5 mm, very particularly preferably in the range 0.3 to 1.5 mm.
  • Films or coatings can be produced by known processes such as spraying, gravure printing, offset printing, curtain casting, spin coating, application by application rollers, brushing or dipping.
  • the flowable mixture of encapsulation material, core material and solvent can be applied to the surface with any type of liquid metering system.
  • the finished, hard encapsulation according to the invention is fixed on the surface.
  • microcapsules produced according to the invention Removing, for example, microcapsules produced according to the invention is only possible through strong mechanical stress.
  • the microcapsules produced by this method cannot be removed by simply bending the surface. Due to the low abrasion of the encapsulation on everyday objects (e.g. cleaning or friction), the core material is released continuously in very small quantities over a long period of time, even without increasing the temperature.
  • a special property of the encapsulation produced according to the invention is that it releases the core material only very slowly at room temperature.
  • the release process can be controlled via the temperature.
  • the very slow thermal release typically takes place in the temperature range from 30 to 90 ° C., preferably in the range from 40 to 70 ° C.
  • the release is largely continuous.
  • the moderate thermal release typically takes place in the temperature range from 50 to 120 ° C., preferably in the range from 80 to 100 ° C. This area is also suitable for causing multiple releases in a cycle-like manner.
  • the rapid, explosive thermal release typically takes place in the temperature range from 120 to 300 ° C., preferably in the range from 140 to 280 ° C., particularly preferably from 180 to 260 ° C. Depending on the duration of use and the proportion of the core material in the encapsulation, multiple releases are also possible here.
  • the thermal release can take place over the entire surface, evenly or via a temperature gradient. Depending on the application, a one-off
  • Release of the core material can be brought about, the precise, targeted release from a single capsule being possible.
  • the encapsulation produced by the method according to the invention can be used for a targeted multiple rapid release of the core material, since the
  • Release can be designed in such a way that not all of the core material is released in one release step, but instead a targeted thermal release can be brought about from the same encapsulation.
  • a targeted thermal release can be brought about from the same encapsulation.
  • an insect repellent can be released from the encapsulation several times if required.
  • the manufacturing process can be carried out as follows, for example:
  • the polymeric film-forming encapsulation material, the core material and the solvent are, if appropriate mixed with little heat and with stirring, preferably homogenized.
  • This flowable mixture can then be applied in a suitable manner to a surface in a controlled manner.
  • the applied mixture then dries on the surface, optionally with a gentle supply of heat, optionally under the influence of a possibly gently heated gas stream, and is fixed on the surface after the drying process.
  • the liquid mixture from Example 1 was applied by means of a piezo metering system in small drops with an average weight of about 7-10 mg to a 0.2 mm thick commercial aluminum foil (8 cm x 18 cm) at regular intervals. A total of 2500 drops with a total weight of 17.5 g were applied in this process.
  • the aluminum foil thus prepared was then dried over a period of 60 minutes using a stream of air at a temperature of about 30 degrees, as a result of which the solvent contained in the formulation was removed. After drying, there were hard, almost odorless drops firmly attached to the aluminum foil, which consisted of 75 parts of encapsulation material and 25 parts of spruce needle oil. It was very difficult to remove the drops from the aluminum foil.
  • the film produced according to Example 2 with the encapsulated spruce needle oil was applied in different living rooms of different sizes to hot water radiators of different sizes, as are common in living rooms. Depending on the set temperatures on the radiators, starting at around 40 ° C, a pleasant spruce scent developed in the rooms. The intensity of the
  • Example 2 the capsules were placed on a commercially available cardboard instead of the
  • Ventilation system released under the influence of heat. This leads to a significant improvement in the cost / usage ratio.
  • Example 6 Various carrier materials (cardboard, aluminum, various plastic materials) were coated with the mixture produced in Example 1 uniformly, covering the entire area with a layer thickness of approximately 1 mm, dried in accordance with the conditions in Example 2 and tested as described in Examples 3 and 4 above , The results achieved here also led to a high level of user acceptance.
  • Example 6 Various carrier materials (cardboard, aluminum, various plastic materials) were coated with the mixture produced in Example 1 uniformly, covering the entire area with a layer thickness of approximately 1 mm, dried in accordance with the conditions in Example 2 and tested as described in Examples 3 and 4 above , The results achieved here also led to a high level of user acceptance.
  • Example 6 Example 6
  • a total of 500 microcapsules containing a lemon oil were applied to the inside of the housing of a hair dryer at the outlet of the hot air stream.
  • the preparation of the mixture of encapsulation material, solvent and lemon oil was carried out as in Example 1.
  • the application was carried out with a metering device (e.g. a pipette) and then the drying according to Example 2.
  • a metering device e.g. a pipette
  • a temperature stable polymeric film for example, polyimide polymers such as Kapton ®, polymer of pyromellitic anhydride and 4,4-diaminodiphenyl ether, trademark of DuPont
  • a thickness of 102 microns were a total of 100
  • Microcapsules containing 5 different perfume oils applied The preparation of the mixture of encapsulation material, solvent and the respective perfume oil was carried out as in Example 1. The application was carried out with a dosing device (e.g. a pipette) and then the drying according to Example 2. The capsule size was chosen so that the fixed encapsulations had a size of about 0.4 to 0.6 mm.
  • a dosing device e.g. a pipette
  • the core material was released eruptively when the encapsulation was rapidly heated to 180 ° C.
  • 150 small holes with a diameter of 1.5 mm were drilled in a commercially available, 1.5 mm thick Pertinax board (20 x 30 mm), as is usually used in electronic circuits. Correspondingly large aluminum sleeves (inner diameter 0.8 mm) were inserted into these drill holes Side were open. 150 mixtures were metered into these openings according to the production process mentioned in Example 1, containing 150 different perfume compositions or fragrances from the areas of fougere, oriental, chypre and floral. 2 mg of the mixture of core material (here: perfume compositions or fragrances), encapsulation material and acetone were metered into each tube.
  • the board prepared in this way was dried as described in Example 2. Subsequently, small electrical heating elements (high-resistance electrical resistors in the form of chromed resistance wires (e.g. Isachrom 60, Conrad electronic)) were attached to the closed side of the aluminum sleeves, which can be controlled individually and briefly a temperature of about 2 to 5 seconds Generated 270 ° C. This process caused an explosive vaporization of the perfume compositions or fragrances. All of the perfume oils and fragrances released by this process were clearly and unmistakably perceptible at a distance of approx. 70 cm. Even more intense fragrance impressions were registered after above the board, i.e. on the open side of the
  • Aluminum sleeves a commercially available axial fan was attached. Instead of aluminum sleeves, sleeves made of VA steel, Teflon, Kapton ® , glass, etc. can also be used.
  • a temperature-stable film with encapsulations containing nicotine was placed in a mobile release device, which the smoker can operate and transport individually.
  • the test was carried out in such a way that all test subjects were equipped with a nicotine vaporizer system worn on the chest over a period of 4 hours, alternating in the morning and in the afternoon, over a period of 4 weeks.
  • the nicotine vaporizer was a preferred one Embodiment around a 6 x 8 x 2 cm device that contained a heater that was powered by built-in batteries. On this heater were on a polyimide film (Kapton ® polyimide polymers, such as, brand name of DuPont) 100 contained about 0.1 mg nicotine heavy capsules.
  • the proportion of the encapsulation material was 90%, ie the nicotine proportion per encapsulation containing nicotine was about 0.01 mg.
  • a trigger unit there was a push button on the evaporator system. The test subjects were asked to briefly press this button if there was a need for smoke. In this case, a heating pulse was generated via the microelectronics built into the device, which heated the heating element to about 250 ° C. under an encapsulation containing nicotine. The vaporizing nicotine escaped from an opening in the upper part of the device. From there, the vaporized nicotine reached the test subjects' respiratory organs.
  • test subjects filled out an assessment sheet daily, in which they wrote about her
  • Smoking or addictive behavior provided information.
  • the evaluation of the questionnaires showed that the smoking or addictive behavior of smokers was strongly influenced overall when using the nicotine vaporizer. Around 80% of smokers said they had cut their cigarette consumption by an average of 70% while they were using the device.
  • the test subjects reduced their daily cigarette consumption, with an increasing tendency also significantly in times without the nicotine vaporizer. Three of the twenty test subjects stopped smoking after the end of the test phase.

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Abstract

La présente invention concerne un procédé pour produire des capsules contenant au moins un polymère filmogène et un matériau de noyau et pour les appliquer sur des surfaces. La présente invention concerne également l'utilisation de ces capsules pour libérer le matériau de noyau.
PCT/EP2002/003155 2001-03-23 2002-03-21 Procede de production de capsules WO2002076605A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE10114509A DE10114509A1 (de) 2001-03-23 2001-03-23 Verfahren zur Herstellung von Einkapselungen
DE10114513 2001-03-23
DE10114513.6 2001-03-23
DE10114509.8 2001-03-23

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WO2002076605A1 true WO2002076605A1 (fr) 2002-10-03

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2177213A1 (fr) 2008-09-17 2010-04-21 Siegfried Generics International AG Granulé contenant de la nicotine

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2055019A1 (en) * 1970-11-09 1972-05-10 The National Cash Register Co., Dayton, Ohio (V.StA.) Micro-capsule coated backing - for applying percutaneous anti-rheumat or anti-varicose preparations without touching by hand
US3870542A (en) * 1969-08-22 1975-03-11 Kanegafuchi Spinning Co Ltd Process of treating fibrous articles with microcapsules containing hydrophobic treating agent
GB1401143A (en) * 1972-04-15 1975-07-16 Eurand Spa Method of treating a fabric
EP0436729A1 (fr) * 1989-08-01 1991-07-17 Kanebo, Ltd. Microcapsules, liquide de traitement et structure textile contenant des microcapsules
FR2781238A1 (fr) * 1998-07-20 2000-01-21 Ted Lapidus Article textile ou vestimentaire ou de toilette et soin du corps, porteur de microcapsules, et procedes pour sa realisation
WO2000069440A2 (fr) * 1999-05-13 2000-11-23 Fluid Technologies Plc Procedes d'apport de nicotine

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3870542A (en) * 1969-08-22 1975-03-11 Kanegafuchi Spinning Co Ltd Process of treating fibrous articles with microcapsules containing hydrophobic treating agent
DE2055019A1 (en) * 1970-11-09 1972-05-10 The National Cash Register Co., Dayton, Ohio (V.StA.) Micro-capsule coated backing - for applying percutaneous anti-rheumat or anti-varicose preparations without touching by hand
GB1401143A (en) * 1972-04-15 1975-07-16 Eurand Spa Method of treating a fabric
EP0436729A1 (fr) * 1989-08-01 1991-07-17 Kanebo, Ltd. Microcapsules, liquide de traitement et structure textile contenant des microcapsules
FR2781238A1 (fr) * 1998-07-20 2000-01-21 Ted Lapidus Article textile ou vestimentaire ou de toilette et soin du corps, porteur de microcapsules, et procedes pour sa realisation
WO2000069440A2 (fr) * 1999-05-13 2000-11-23 Fluid Technologies Plc Procedes d'apport de nicotine

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2177213A1 (fr) 2008-09-17 2010-04-21 Siegfried Generics International AG Granulé contenant de la nicotine
US10413512B2 (en) 2008-09-17 2019-09-17 Siegfried Ltd. Nicotine-containing granulate

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